JP3461405B2 - Oil-in-water emulsion cosmetic - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oil-in-water type emulsified cosmetic composition having a high UV protection effect and excellent water repellency and durability.

[0002]

2. Description of the Related Art Conventionally, cosmetics for the purpose of protecting ultraviolet rays have been blended with inorganic powders such as zinc oxide and titanium oxide.

However, there is a problem that the inorganic powder such as zinc oxide and titanium oxide becomes white when the compounding amount is increased in order to obtain a sufficient UV protection effect, and the appearance after makeup is impaired. Further, zinc oxide and titanium oxide have a strong photocatalytic activity, and there is also a problem that organic substances of other compounding components are decomposed. For the purpose of solving this, many techniques for coating the surface of particles with a silicon compound to eliminate the activity have been proposed (Japanese Patent Laid-Open No. 63-113081, etc.), but these methods also completely eliminate the activity. The current situation is that it cannot be done.

On the other hand, the oil-in-water emulsified cosmetic composition is characterized in that it has a less oily feel and is excellent in use since the continuous phase is composed of an aqueous component. However, the oil-in-water emulsified cosmetic composition has drawbacks in that it is inferior in durability and water repellency and easily loses makeup as compared with the water-in-oil emulsified cosmetic composition.

[0005]

SUMMARY OF THE INVENTION Therefore, an object of the present invention is to provide an oil-in-water type emulsion cosmetic which is excellent in UV protection effect, stable in appearance after makeup, and stable in water repellency and durability. To provide.

[0006]

Under such circumstances, the inventors of the present invention have conducted intensive studies and found that a particle of a specific double oxide having a perovskite type structure or a solid solution thereof is combined with an acrylic acid-based polymer. It was found that an oil-in-water emulsified cosmetic composition having high UV protection ability and stability, and excellent water repellency and durability can be obtained by using it, and completed the present invention.

That is, the present invention provides the following components (a) and (b): (a) A perovskite structure represented by the general formula ABO ₃ (where A and B are metallic elements and O is an oxygen element). Particles having a volume average particle size of 1 μm or less and a crystallite size by X-ray diffraction of from 150 to 300 Å, and (b) UV protection containing an acrylic acid-based polymer. An oil-in-water emulsion cosmetic for use is provided.

The component (a) used in the present invention is a complex oxide having a perovskite structure represented by the general formula ABO ₃ (A, B and O have the same meanings as described above) or a solid solution thereof. Here, the perovskite type structure is one of typical crystal structures generally found in an inorganic compound whose composition is represented by ABX ₃ , and is a perovskite C.
Besides aTiO ₃ , many compounds have this structure. Since the component (a) of the present invention is a double oxide, it has the general formula ABO
It can be represented by ₃ .

In the general formula ABO ₃ , the metal element represented by A is preferably an oxygen 12-coordinated metal element, and particularly selected from the group consisting of Ca, Sr, Ba, Pb and rare earth elements such as La and Ce. One or more oxygen 12-coordinated metal elements are preferable, more preferably Ca, Sr and La,
It is a rare earth metal element such as Ce.

In the general formula ABO ₃ , the metal element represented by B is preferably an oxygen hexacoordinate metal element, such as Ti, Zr, Hf, Sn, W, Nb, Ta,
Examples thereof include Cr, Mo, Mn, Al, and Zn. Of these, one or more oxygen hexacoordinated metal elements selected from the group consisting of Ti, Zr, and Group IVa elements of Hf are particularly preferable, and Ti and Zr are more preferable.

In the above, one or more kinds of metal elements may be contained as the metal elements represented by A and B because the component (a) contains a solid solution of a double oxide. That is, it may be a solid solution having a structure in which some of the metal elements of A and B are replaced with other metal elements of A and B, respectively.

The complex oxide of the component (a) of the present invention or its solid
The specific composition of the solution is, for example, Ca (Ti, Z
r) O₃(Compound of A = Ca, B = Ti, Zr in the general formula
Means The same applies hereinafter. ), (Ca, Sr)
TiO₃, CaTiO₃, SrTiO₃, BaTi
O₃, CaZrO₃, SrZrO₃, (Ca, Sr) Z
rO ₃, (Ca, Sr) (Ti, Zr) O₃, (Ca,
La) TiO₃, (Ca, Ce) TiO₃, (Ca, C
e) (Ti, Zr) O₃Etc. These
Especially, Ca (Ti, Zr) O₃, (Ca, Sr) Ti
O₃, (Ca, Ce) TiO₃, (Ca, Ce) (T
i, Zr) O₃Is preferred.

The component (a) of the present invention has a perovskite structure which is not known in the conventional ultraviolet absorbers.
Even with such a crystal structure, the value of the band gap energy can be a value that is convenient for the absorption of ultraviolet rays, and thus a high ultraviolet absorption ability can be obtained. That is, since it is known that ceramics do not have a continuous valence band and conduction band, they absorb light having a wavelength corresponding to energy equal to or higher than the band gap energy which is the energy difference between the two levels.
High permeation of ultraviolet light is obtained even with the perovskite structure. It is also known that many compounds having a perovskite structure have low photocatalytic activity.

The volume average particle diameter of the particles of the composite oxide of component (a) or its solid solution must be 1 μm or less, preferably 0.1 to 0.4 μm. When the volume average particle diameter exceeds 1 μm, the surface area becomes small, so that the ultraviolet absorption ability becomes insufficient and the transparency in the visible light region tends to become insufficient. The volume average particle diameter is a value obtained by volume average from the particle size distribution measured by a particle size distribution measuring device.

The particles of the mixed oxide of component (a) or its solid solution have a crystallite size of 150 to 3 by X-ray diffraction.
It should be 00 angstroms, preferably 170-250 angstroms. If it exceeds 300 angstroms, the ultraviolet absorption capacity tends to be insufficient in relation to the wavelength of ultraviolet rays. On the other hand, if it is less than 150 Å, it tends to have an insufficient ultraviolet absorbing ability because it approaches an amorphous structure. Here, the crystallite size (D _hkl ) by X-ray diffraction is the main peak (for example, CaTiO ₃₎ obtained from the X-ray diffraction pattern of the sample powder.
Then, the full width at half maximum of the surface index (121) is calculated as
It can be obtained by introducing it into the r formula.

[0016]

## EQU1 ## D _hkl = kλ / β cos θ (where constant k = 0.9, λ = 1.5406 (Å), β
Indicates the half width of the peak. )

The complex oxide of the component (a) or the solid solution particles thereof used in the present invention has a reflectance spectrum measured by using a tablet sample in which 1 part by weight of the component (a) and 19 parts by weight of barium sulfate are mixed. The average absorbance in the ultraviolet region of 250 to 380 nm is preferably 0.6 or more, more preferably 0.7 to 1.2.

When the reflectance spectrum of the component (a) is measured using a tablet sample in which 1 part by weight of the component (a) and 19 parts by weight of barium sulfate are mixed, the reflectance at 500 nm is 85% or more. Preferably, more preferably 9
It is 0 to 100%. Thus, the visible light wavelength of 500
A high reflectance at nm results in less absorption at that wavelength and greater transparency in the visible region.

Any method can be used for producing the composite oxide of the component (a) as long as it is a method of synthesizing a perovskite type composite oxide. For example, a solid oxide obtained by calcining a mixture of carbonate and hydroxide can be used. Phase method, obtained by calcining a precipitate obtained by a liquid phase method in which an aqueous solution or alcohol solution of chloride, nitrate, sulfate, etc. of each composition component is mixed with an aqueous solution or alcohol solution of soluble alkali, oxalic acid, etc. Examples of the method include, but are not limited to, a method obtained by subjecting a hydroxide obtained by a liquid phase method to a hydrothermal treatment, a gas phase method such as a CVD method or a spray pyrolysis method, and the like.

In these methods, the volume average particle size and crystallite size specified in the present invention can be prepared, for example, by precipitating the oxalate salt from the aqueous solution of each salt and the aqueous solution of oxalic acid. , Oxalic acid aqueous solution at 60 ℃
It is preferable to heat the solution as above and drop the compositional salt aqueous solution into this aqueous solution. The calcination temperature of the obtained oxalate is 5
The temperature is preferably 00 to 900 ° C. In the spray pyrolysis method,
Each salt aqueous solution is made into a mist by an ultrasonic atomizer or the like, and N ₂ gas is introduced into the reaction tube as a carrier gas. The gas flow rate may be 2 to 8 l / min, and the reaction temperature may be 600 to 1000 ° C.

The particles of the composite oxide of component (a) or the solid solution thereof can be used alone or in combination of two or more kinds, and the blending amount can be arbitrarily selected according to the dosage form. It is preferable to add 0.1 to 50% by weight of the total composition, and particularly preferably 1 to 25% by weight, and more preferably 5 to 10% by weight, because higher UV protection ability can be obtained.

The acrylic acid-based polymer of the component (b) used in the present invention is not particularly limited as long as it forms a gel by neutralizing with an alkali agent, and is generally called a water-soluble alkali thickening polymer. What is used is used. Examples of such acrylic acid polymers include B.I. F. Carbopol 907, 91 commercially available from BFGoodrich Company
0, 934, 934-P, 940, 941, 954, 9
80, 981, 1342, 1382, 2984, 598
4 and Pemulen TR-1, TR-2, etc. commercially available from Lipo Chemicals inc.
(Hypam) SA-100H, SR-150H, SS-20
AQUPEC HV-501, HV-504, HV commercially available from Sumitomo Seika Co., Ltd.
-505 etc. are mentioned. Among these, particularly preferred acrylic acid-based polymers include Carbopol 941 and
1342; Pemulan TR-1 and TR-2.

The acrylic acid-based polymer as the component (b) may be used alone or in combination of two or more kinds, and the compounding amount may be appropriately determined depending on the kind of the polymer, etc. It is preferable to add 0.1 to 20% by weight in the composition, particularly 0.1 to 1% by weight, and further 0.15 to
A blending amount of 0.3% by weight is preferable because stability and a feeling of use are excellent.

The alkaline agent for neutralizing and gelling the acrylic acid-based polymer is, for example, sodium hydroxide,
Examples thereof include inorganic bases such as potassium hydroxide and ammonium hydroxide, and organic bases such as triethanolamine and L-arginine, which may be blended as necessary depending on the blending amount of the acrylic acid polymer.

If desired, the oil-in-water emulsion cosmetic of the present invention may further contain other UV protective agents, that is, UV absorbers or UV scattering agents, to obtain a higher UV protective effect. Among these, as the ultraviolet absorber, those commonly used in ordinary skin external preparations can be used, and typical compounds of the ultraviolet absorber include the following.

(1) Benzoic acid derivative system: para-aminobenzoic acid (PABA), PABA monoglycerin ester,
N, N-dipropoxy PABA ethyl ester, N, N
-Diethoxy PABA ethyl ester, N, N-dimethyl PABA ethyl ester, N, N-dimethyl PABA
Butyl ester, N, N-dimethyl PABA amyl ester, N, N-dimethyl PABA octyl ester and the like.

(2) Anthranilic acid derivative system: homomenthyl-N-acetylanthranilate, etc.

(3) Salicylic acid derivative system: amyl salicylate, menthyl salicylate, homomenthyl salicylate, octyl salicylate, phenyl salicylate,
Benzyl salicylate, p-isopropanol phenyl salicylate and the like.

(4) Cinnamic acid derivative system: octyl cinnamate, ethyl-4-isopropyl cinnamate, methyl-2,5-diisopropyl cinnamate, ethyl-2,
4-diisopropyl cinnamate, methyl-2,4-diisopropyl cinnamate, propyl-p-methoxycinnamate, isopropyl-p-methoxycinnamate, isoamyl-p-methoxycinnamate, octyl-p-methoxycinnamate (2- Ethylhexyl-p
-Methoxycinnamate), 2-ethoxyethyl-p-
Methoxycinnamate, cyclohexyl-p-methoxycinnamate, ethyl-α-cyano-β-phenylcinnamate, 2-ethylhexyl-α-cyano-β-phenylcinnamate, glyceryl mono-2-ethylhexanoyl-diparamethoxy Thinnamate etc.

(5) Benzophenone derivative system: 2,4-
Dihydroxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ',
4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-4'-methylbenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonate, 4-phenyl Benzophenone, 2-ethylhexyl-4'-phenyl-benzophenone-2-carboxylate, 2-hydroxy-4-n-octoxybenzophenone, 4-hydroxy-3-carboxybenzophenone and the like.

(6) Other UV absorbers: 3- (4 '
-Methylbenzylidene) -d, 1-camphor, 3-benzylidene-d, 1-camphor, urocanic acid, urocanic acid ethyl ester, 2-phenyl-5-methylbenzoxazole, 2,2'-hydroxy-5-methyl Phenylbenzotriazole, 2- (2'-hydroxy-
5'-t-octylphenyl) benzotriazole, dibenzalacin, dianisoylmethane, 4-methoxy-
4'-t-butyldibenzoylmethane, 5- (3,3 '
-Dimethyl-2-norbornylidene) 3-pentane-2
-One, 1- (3,4-dimethoxyphenyl) -4,
4'-dimethyl-1,3-pentadione and the like.

Among the above, particularly preferable ultraviolet absorbers include 2-ethylhexyl-p-methoxycinnamate, 4-methoxy-4'-t-butyldibenzoylmethane and the like.

Examples of the ultraviolet scattering agent include inorganic powders such as titanium oxide, zinc oxide, iron oxide, kaolin, talc, mica, barium sulfate, alumina and silica, nylon powder, polymethylmethacrylate and polymethylsilsesqui. Organic powder such as oxane can be mentioned,
Fine particle titanium oxide, which has both ultraviolet scattering ability and absorbing ability,
Metal oxides such as particulate zinc oxide and flaky zinc oxide are particularly preferred. Here, the fine particle titanium oxide and zinc oxide have an average particle size of about 10 to 100 nm, and commercially available products can be used as they are. On the other hand, flaky zinc oxide has an average particle size of 1
It has a plate shape ratio of 3 or more with a thickness of 10 to 1000 nm and a thickness of 10 to 200 nm, and examples thereof include those manufactured by the method described in JP-A-1-175921. In addition, these ultraviolet scattering agents may be used in combination for the purpose of improving effects such as dispersibility and touch. As a composite ultraviolet scattering agent, Japanese Patent Laid-Open No. 63-132821,
JP-A-1-190625, JP-A-4-10429
No. 3, JP 4-196757 A, JP 4-
Examples thereof include those described in Japanese Patent No. 142083.

Further, these ultraviolet scattering agents can be blended in the oil-in-water emulsion cosmetic of the present invention as they are, but for the purpose of further enhancing water repellency and oil repellency, methylhydrogen polyacrylate is used by a known method. Silicone treatment with siloxane, trimethylsiloxysilicic acid, methyl polysiloxane, etc., fluorine treatment with perfluoroalkyl phosphate ester, etc., lecithin treatment, metal soap treatment,
It can also be used after being subjected to a surface treatment such as an alkyl phosphate treatment.

These UV protective agents may be used alone or in combination of two or more, and the blending amount may be appropriately selected depending on the application, but usually it is 0.
It is preferably blended in an amount of 1 to 50% by weight, particularly preferably 1 to 25% by weight, more preferably 3 to 10% by weight since a higher UV protection ability can be obtained.

The oil-in-water emulsion cosmetic of the present invention also comprises
It is preferable to add a water-soluble polymer, if necessary, because the emulsion stability and feel are further improved. The water-soluble polymer used here is not particularly limited as long as it is used in ordinary cosmetics, and for example, guar gum, quince seed, carrageenan, locust bean gum, gum arabic, tragacanth, pectin, mannan, starch. , Sodium alginate, sodium hyaluronate,
Xanthan gum, pullulan dextran, curdlan,
Collagen, keratin, casein, albumin, gelatin, chondroitin sulfate, chitin, cationized cellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxypropylmethylcellulose, hydroxyethylcellulose, hydroxypropyltrimethylammonium chloride ether, carboxymethylcellulose, dextran sulfate, carboxymethylchitin , Soluble starch, carboxymethyl starch, propylene glycol alginate, polyvinyl alcohol,
Examples thereof include polyvinylpyrrolidone, sodium polyacrylate, polyvinyl methyl ether, polyethylene glycol and the like. Especially preferred water-soluble polymers are
Examples include xanthan gum, sodium hyaluronate, hydroxyethyl cellulose and the like. These water-soluble polymers can be used alone or in combination of two or more,
It is preferably blended in an amount of 0.01 to 5.0% by weight, particularly 0.05 to 3.0% by weight, and more preferably 0.05 to 0.
3% by weight is preferred.

Since the cosmetic of the present invention is an oil-in-water type emulsion cosmetic, it requires water, an oily substance such as an oily base and a surfactant. Water is preferably added in an amount of 10 to 95% by weight, particularly 40 to 80% by weight, based on the total composition. The oily base used in the present invention may be any one used in ordinary cosmetics, for example, hydrocarbon oils such as squalane, liquid paraffin, vaseline; waxes such as whale wax, carnauba wax; jojoba oil. Ester oils such as octyldodecyl myristate and neopentyl glycol dioctanoate; natural animal and vegetable oils such as olive oil and macadamia nut oil; diglyceride and silicone oil. These oily bases can be used alone or in combination of two or more, and 0.1 to 40% by weight in the whole composition,
It is particularly preferable to add 0.1 to 20% by weight.

Any surface active agent may be used as long as it is used in ordinary cosmetics, for example, polyoxyethylene alkyl ether, polyoxyethylene fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol. Examples thereof include fatty acid esters, polyoxyethylene hydrogenated castor oil alkyl sulfates, polyoxyethylene alkyl sulfates, alkyl phosphates, polyoxyethylene alkyl phosphates, fatty acid alkali metal salts, sorbitan fatty acid esters, and glycerin fatty acid esters. These surfactants may be used either individually or in combination of two or more, and are preferably added in an amount of 0.05 to 3% by weight, particularly preferably 0.05 to 2% by weight, based on the total composition.

Further, the oil-in-water emulsion cosmetic of the present invention contains, in addition to the above-mentioned components, components used in ordinary cosmetics, such as alcohols, viscosity modifiers, and stabilizers, as long as the effects of the present invention are not impaired. Agents, humectants, moisturizers, intercellular lipids (ceramide, etc.), preservatives, pH adjusters, antioxidants,
Thickeners, powders, pigments, fragrances, medicinal ingredients, whitening agents and the like can be appropriately added.

As the moisturizing agent, sorbitol,
Xylitol, glycerin, maltitol, propylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, sodium pyrrolidonecarboxylate,
Lactic acid, sodium lactate, polyoxypropylene fatty acid ester, polyethylene glycol and the like can be mentioned.

The oil-in-water emulsified cosmetic composition of the present invention can be produced by a conventional method, and can be made into various dosage forms of oil-in-water emulsified cosmetic compositions such as emulsions, creams, ointments and foundations.

[0042]

The oil-in-water emulsified cosmetic composition of the present invention has a high UV protection ability and stability, is excellent in water repellency and sustainability, and has a good usability.

[0043]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples. In addition, a method for producing a complex oxide and a solid solution thereof is also shown as a synthesis example. Moreover, evaluation of each data in the synthesis example was performed by the following method.

(1) Volume average particle size: A sample powder is dispersed in a 0.1% by weight aqueous solution of sodium polyacrylate (trade name; Poise 530), and a particle size distribution measuring device (manufactured by Horiba, Ltd .; Model LA-700) is used. The volume average was obtained from the particle size distribution measured by.

(2) Crystallite size: The full width at half maximum of the main peak obtained from the X-ray diffraction pattern of the sample powder is determined by the above S
It was determined by introducing it into the Cherrer formula.

(3) Ultraviolet absorption capacity: A total of 2.0 g of sample powder 0.1 g and barium sulfate powder 1.9 g was thoroughly mixed in an agate mortar to prepare a tablet sample, which was then analyzed by a spectrophotometer (manufactured by Hitachi Ltd .; type U). -4000 type), 190-700
The reflection spectrum in the wavelength range of nm was measured, the obtained spectrum was converted into absorbance, and the average absorbance in the ultraviolet region of 250 to 380 nm was calculated and used as the evaluation standard.

(4) Transparency in the visible light region: The reflectance at 500 nm of the reflection spectrum obtained by the above-mentioned measurement of the ultraviolet absorptivity was used as the evaluation standard.

Synthesis Example 1 Calcium chloride 1 × 10 ^-1 mol, titanium chloride 9.5 × 1
0 ^-2 mol and 5 x 10 ^-3 mol of zirconium oxychloride were dissolved in 400 ml of deionized water. Then, 2 × 10 ^-1 mol of oxalic acid was dissolved in 400 ml of ion-exchanged water, this solution was heated to 100 ° C. with stirring, the above chloride aqueous solution was added for 20 seconds, and stirring was continued for 10 minutes. Aqueous potassium solution was added for neutralization, and the mixture was aged for 5 hours. After aging, the precipitate was filtered, washed and dried at 100 ° C.
The obtained powder was pulverized and then calcined at 700 ° C. for 1 hour to obtain a target double oxide powder.

From the X-ray diffraction pattern, the obtained powder was
It was found to be a perovskite type structure represented by Ca (Ti, Zr) O ₃ . The powder had a volume average particle diameter of 0.3 μm, a crystallite size of 210 Å, an ultraviolet absorption capacity of 0.75 and a transparency of 93%.

Synthesis Example 2 The same operation as in Synthesis Example 1 was performed except that the calcination temperature was set to 900 ° C. From the X-ray diffraction pattern, the obtained powder was C
It was found to be a perovskite type structure represented by a (Ti, Zr) O ₃ . The powder had a volume average particle size of 0.35 μm, a crystallite size of 240 Å, an ultraviolet absorption capacity of 0.65 and a transparency of 92%.

Synthesis Example 3 Calcium chloride 2 × 10 ^-3 mol, titanium chloride 1.9 × 1
0 ⁻³ mol and 1 × 10 ⁻⁴ mol of zirconium oxychloride were dissolved in 1000 ml of a 0.1 mol / l hydrochloric acid aqueous solution. This aqueous solution was made into an atomizer by an ultrasonic atomizer, and N ₂ gas was used as a carrier gas at a gas flow rate of 4 l / min to 800 ° C.
The mixed oxide powder was introduced into a reactor heated to 1, and pyrolyzed to obtain a target double oxide powder. The powder obtained here is
From the X-ray diffraction pattern, it was found to be a perovskite structure represented by Ca (Ti, Zr) O ₃ . This powder had a volume average particle diameter of 0.27 μm, a crystallite size of 250 Å, and an ultraviolet absorption capacity of 0.
The transparency was 70 and the transparency was 90%.

Synthetic Example 4 Same as Synthetic Example 1 except that 9.5 × 10 ^-2 mol of calcium chloride, 5 × 10 ^-3 mol of strontium chloride and 1 × 10 ^-1 mol of titanium chloride were dissolved in 400 ml of deionized water. The operation was performed. From the X-ray diffraction pattern, the obtained powder was found to have a perovskite structure represented by (Ca, Sr) TiO ₃ . The powder had a volume average particle size of 0.4 μm, a crystallite size of 225 Å, an ultraviolet absorption capacity of 0.60, and a transparency of 9
It was 3.5%.

Synthesis Example 5 1 × 10 ⁻¹ mol of calcium chloride and 1 × 10 ^{1 of} titanium chloride
^-1 mol was dissolved in 400 ml of deionized water. Then, 2 × 10 ^-1 mol of oxalic acid was dissolved in 400 ml of ion-exchanged water, the solution was heated to 100 ° C. with stirring, the chloride aqueous solution was added for 20 seconds, and stirring was continued for 10 minutes. Aqueous potassium carbonate solution was added for neutralization and aging for 5 hours. After aging, the precipitate was filtered, washed and dried at 100 ° C. The obtained powder was pulverized and then calcined at 700 ° C. for 1 hour to obtain a target double oxide powder. The powder obtained is X
From the line diffraction pattern, it was found that the structure was a perovskite type structure represented by CaTiO ₃ . The powder has a volume average particle size of 0.33 μm and a crystallite size of 21.
The film had a thickness of 5 Å, an ultraviolet absorption capacity of 0.72, and a transparency of 89.5%.

Synthesis Example 6 Strontium chloride 1 × 10 ⁻¹ mol, titanium chloride 1 × 1
0 ^-1 mole ion-exchange water 300ml and ethyl alcohol 1
It was dissolved in a mixed solution of 00 ml. Then oxalic acid 2x1
0 ^-1 mol was dissolved in 400 ml of ethyl alcohol, this solution was heated to 70 ° C with stirring, the above chloride aqueous solution was added for 20 seconds, and stirring was continued for 10 minutes. Aged and aged for 5 hours. After aging, the precipitate was filtered, washed and dried at 100 ° C. The obtained powder was pulverized and then calcined at 800 ° C. for 1 hour to obtain a target double oxide powder. From the X-ray diffraction pattern, the obtained powder was
It was found to be a perovskite type structure represented by SrTiO ₃ . The powder had a volume average particle size of 0.65 μm, a crystallite size of 250 Å, an ultraviolet absorption capacity of 0.60, and a transparency of 88.8%.

Synthesis Example 7 The same operation as in Synthesis Example 6 was performed except that strontium chloride was changed to parium chloride. From the X-ray diffraction pattern, the obtained powder was found to have a perovskite structure represented by BaTiO ₃ . The volume average particle size of the powder is 0.53 μm, the crystallite size is 245 Å, the ultraviolet absorption capacity is 0.65, and the transparency is 9.
It was 2.7%.

Synthesis Example 8 9.5 × 10 ⁻² mol of calcium chloride and 5 × cerium chloride
10 ⁻³ mol and 1 × 10 ⁻¹ mol of titanium chloride were dissolved in 400 ml of deionized water. Then, oxalic acid 2 × 10 ^-1
Dissolve the moles in 400 ml of ion-exchanged water, heat the solution to 100 ° C. with stirring, add the above chloride aqueous solution for 20 seconds and continue stirring for 10 minutes, and then add potassium carbonate aqueous solution for neutralization. And aged for 5 hours. After aging, the precipitate was filtered, washed and dried at 100 ° C. The obtained powder was pulverized and then calcined at 700 ° C. for 1 hour to obtain a target double oxide powder. From the X-ray diffraction pattern, the obtained powder was
It was found to be a perovskite type structure represented by (Ca, Ce) TiO ₃ . The powder had a volume average particle size of 0.35 μm, a crystallite size of 205 Å, an ultraviolet absorption capacity of 0.75, and a transparency of 90%.
Met.

Synthesis Example 9 3 × 10 ⁻¹ mol of calcium chloride and 3 × 10 6 of titanium chloride
^-1 mol was dissolved in 300 ml of deionized water. Then 4
Ion-exchanged water 4 in 130 g of 8% sodium hydroxide aqueous solution
The aqueous solution containing 0 g was heated to 40 ° C. with stirring, the chloride aqueous solution was added dropwise at 5 ml / min, and aged for 1 hour. After completion of the aging, ion-exchanged water was added so that the slurry concentration (CaTiO ₃ conversion) was reached. Then, 600 ml of the obtained slurry was dispensed into a stainless steel 1 liter container and subjected to hydrothermal treatment at 150 ° C. for 5 hours while stirring. After the treatment was completed, the product was filtered, thoroughly washed, and then dried at 100 ° C. to obtain a target double oxide powder. The obtained powder shows that the CaTi
It was found to be a perovskite structure represented by O ₃ . The volume average particle size of this powder is 0.87μ.
m 2, the crystallite size was 270 Å, the ultraviolet absorption capacity was 0.63, and the transparency was 87%.

Synthesis Example 10 Calcium chloride 1 × 10 ^-1 mol, titanium chloride 7.5 × 1
0 ^-2 mol and 2.5 x 10 ^-2 mol of zirconium oxychloride were dissolved in 400 ml of deionized water. Then, 2 × 10 ^-1 mol of oxalic acid was dissolved in 400 ml of deionized water,
The solution was heated to 100 ° C. with stirring, the above chloride aqueous solution was added dropwise over 10 minutes, and the stirring was continued for 10 minutes. Then, an aqueous potassium carbonate solution was added to neutralize and aged for 5 hours.
After aging, the precipitate was filtered, washed and dried at 100 ° C. After pulverizing the obtained powder, calcination at 700 ° C. for 1 hour,
The target double oxide powder was obtained. From the X-ray diffraction pattern, the obtained powder was found to have a perovskite structure represented by Ca (Ti, Zr) O ₃ . The powder has a volume average particle size of 0.45 μm, a crystallite size of 240 Å, and an ultraviolet absorption capacity of 0.6.
2. The transparency was 92.5%.

Synthesis Example 11 Cerium chloride was changed to lanthanum chloride, and the calcination temperature was 800 ° C.
The same operation as in Synthesis Example 8 was performed except that The obtained powder shows that (Ca, La) TiO 2
It was found to have a perovskite structure represented by ₃ . The volume average particle size of this powder is 0.33 μm.
The crystallite size was 202 Å, the ultraviolet absorption capacity was 0.73, and the transparency was 94%.

Synthesis Example 12 9.5 × 10 ^-2 mol of calcium chloride and 5 × of cerium chloride
10 ⁻³ mol, 9.5 × 10 ⁻² mol of titanium chloride and 5 × 10 ⁻³ mol of zirconium oxychloride were added to 25 ml of ion-exchanged water.
It was dissolved in a mixed solution of 0 ml and 150 ml of isopropyl alcohol. Then, 2 × 10 ^-1 mol of oxalic acid was dissolved in 400 ml of isopropyl alcohol, the solution was heated to 80 ° C. with stirring, the chloride aqueous solution was added dropwise in 30 minutes, and stirring was continued for 10 minutes after completion of the addition. Then, it was neutralized with aqueous ammonia and aged for 2 hours. After completion of aging, the precipitate was filtered and washed, and vacuum dried at 80 ° C. The obtained powder was pulverized and then calcined at 700 ° C. for 1 hour to obtain a target double oxide powder. From the X-ray diffraction pattern, the obtained powder was (C
It was found to be a perovskite type structure represented by a, Ce) (Ti, Zr) O ₃ . The powder had a volume average particle size of 0.29 μm, a crystallite size of 215 Å, an ultraviolet absorption capacity of 0.75, and a transparency of 89.1%.

Example 1 An oil-in-water type emulsion cosmetic having the composition shown in Table 1 was produced by a conventional method. The obtained cosmetics were evaluated for UV protection effect, stability, durability, water repellency and feeling of use. The results are shown in Table 1.
Shown in.

(Evaluation method) (1) UV protection effect, durability, water repellency and feeling of use: Sensory evaluation was performed by having 20 professional panelists use each cosmetic for one month. The results are shown according to the following criteria. ◎: 16 to 20 people answered that they were good. ○: 11 to 15 people answered that they were good. Δ: 6 to 10 people answered that they were good. ×: 0 to 5 people answered that they were good.

(2) Stability: After each cosmetic was stored at 50 ° C. for 1 month, its condition was visually evaluated according to the following criteria. ⊚: No change in state is observed. ◯: Some change in condition is recognized. Δ: A large change is recognized in the state. X: Separation is recognized.

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[Table 1]

Example 2 (Emulsion) An emulsion having the following composition was produced by a conventional method. The obtained emulsion showed good results in ultraviolet protection effect, emulsion stability, sustainability, water repellency and feeling of use.

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[Table 2] (Component) (% by weight) Double Oxide Powder (Synthesis Example 4) 10.0 Cetanol 1.0 Squalane 5.0 Olive oil 8.0 Jojoba oil 2.0 Acrylic acid polymer (Pemlan TR-2) 0.1 Acrylic acid polymer (Carbopol 941) 0.1 Xanthan gum 0.1 2-ethylhexyl-p-methoxycinnamate 3.0 4-Methoxy-4'-t-butyldibenzoylmethane 3.0 Butylparaben 0.1 Methylparaben 0.1 Ethanol 3.0 Glycerin 2.0 1,3-butylene glycol 2.0 L-arginine 0.2 Perfume 0.1 Purified water balance

Example 3 (Cream) A cream having the following composition was produced by a conventional method. The obtained cream showed good results in UV protection effect, emulsion stability, sustainability, water repellency and feeling of use.

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[Table 3] (Component) (% by weight) Double Oxide Powder (Synthesis Example 6) 10.0 Stearic acid 2.0 Cetanol 1.0 Cholesterol 1.0 Squalane 10.0 Olive oil 5.0 Jojoba oil 5.0 Acrylic acid polymer (Pemlan TR-1) 0.2 Acrylic acid polymer (Carbopol 1342) 0.2 Xanthan gum 0.1 Hydroxyethyl cellulose 0.1 2-ethylhexyl-p-methoxycinnamate 3.0 4-Methoxy-4'-t-butyldibenzoylmethane 3.0 Butylparaben 0.1 Methylparaben 0.1 Glycerin 10.0 L-arginine 0.4 Perfume 0.1 Purified water balance

Example 4 (Liquid foundation) A liquid foundation having the following composition was produced by a conventional method. The obtained liquid foundation showed good results in terms of UV protection effect, emulsion stability, sustainability, water repellency and usability.

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[Table 4] (Component) (% by weight) Double Oxide Powder (Synthesis Example 11) 10.0 Squalane 5.0 Octyldodecyl myristate 5.0 Microcrystalline Wax 6.0 Acrylic acid polymer (Pemlan TR-2) 0.1 Acrylic acid polymer (Carbopol 941) 0.1 Carboxymethyl cellulose 0.1 2-ethylhexyl-p-methoxycinnamate 3.0 4-Methoxy-4'-t-butyldibenzoylmethane 3.0 Butylparaben 0.1 Methylparaben 0.1 Glycerin 10.0 Kaolin 10.0 Talc 10.0 Coloring pigment 15.0 L-arginine 0.2 Fragrance 0.2 Purified water balance

Example 5 (Aerosol Cosmetic) An aerosol cosmetic having the following composition was produced by a conventional method.
The obtained aerosol cosmetics showed good results in ultraviolet protection effect, emulsion stability, sustainability, water repellency and usability.

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[Table 5] (Component) (% by weight) Double oxide powder (Synthesis example 12) 5.0 Isopropyl myristate 2.0 Acrylic acid polymer (Pemlan TR-2) 0.1 Butylparaben 0.1 Methylparaben 0.1 Glycerin 10.0 Talc 1.0 L-arginine 0.1 Fragrance 0.2 LPG / dimethyl ether mixed gas (8/2) 7.0 Purified water balance Made

─────────────────────────────────────────────────── ─── Continuation of front page (72) Inventor Kazuhiro Yamaki 2-1-3 Fumika, Sumida-ku, Tokyo Kao Co., Ltd. Research Institute (72) Inventor Yuji Suzuki 2-1-3 Fumika, Sumida-ku, Tokyo Kao Co., Ltd. In-house research institute (56) Reference Japanese Unexamined Patent Publication No. 5-339121 (JP, A) Edited by Japan Cosmetic Engineers Association, Cosmetic Science Guidebook, Japan, Japan Cosmetic Engineers Association, May 26, 1979, 46th to 47th , Nos. 418-419, "2.4.3 Main ingredients used in emulsions", "1.2.3 (2) Water phase components", Takeo Tamura, Cosmetic Science, (Company) Japan Hair Science Association, October 10, 1977, 3rd edition, 210, (17) Sodium polyacrylate (58) Fields investigated (Int.Cl. ⁷ , DB name) A61K 7/00 A61K 7/42 C09K 3/00

Claims (5)

(57) [Claims] 1. The following components (a) and (b): (a) Double oxidation having a perovskite structure represented by the general formula ABO ₃ (where A and B are metallic elements and O is an oxygen element). Or a solid solution thereof having a volume average particle diameter of 1 μm or less and a crystallite size by X-ray diffraction of 150 to 300 Å, (b) an oil-in-water emulsion for UV protection containing an acrylic acid polymer Cosmetics. 2. The oil-in-water type ultraviolet protective oil according to claim 1, wherein the component (a) in the general formula ABO ₃ is A is an oxygen 12-coordinated metal element and B is an oxygen 6-coordinated metal element. Emulsified cosmetics. 3. The component (a) is a compound of the general formula ABO ₃ in which A is selected from Ca, Sr, Ba, Pb and rare earth elements, and B is selected from Ti, Zr and Hf. Item 1. An oil-in-water type emulsion cosmetic for protection against ultraviolet rays according to Item 1. 4. The average absorbance in the ultraviolet region of 250 to 380 nm is 0.6 or more by reflection spectrum measurement of a tablet sample in which 1 part by weight of the component (a) is mixed with 19 parts by weight of barium sulfate. The oil-in-water type emulsion cosmetic for ultraviolet protection according to any one of claims 1 to 3, wherein 5. The component (a) has a reflectance of 85% or more at 500 nm measured by a reflection spectrum of a tablet sample in which 1 part by weight of the component (a) and 19 parts by weight of barium sulfate are mixed. The oil-in-water type emulsion cosmetic for ultraviolet protection according to any one of 1 to 4.